Novel basic indoline dyestuffs

ABSTRACT

1. BASIC DYESTUFF OF THE FORMULA   (1-R3,2-((2-R1,3,3-DI(H3C-),5-R-INDOLIN-1-YL)-CH=C(-R2)-),   3,3-DI(H3C-),5-R4-INDOLE)(+) AN(-)   WHEREIN R AND R4, INDEPENDENTLY OF EACH OTHER, ARE HYDROOGEN, ALKYL OF 1-6 CARBON ATOMS, CYCLOPENTYL, CYCLOHEXYL, PHENYL, NAPHTHYL, PHENYLALKYL OF 1-6 CARBON ATOMS IN THE ALKYL PORTION, ALKOXY OF 1-6 CARBON ATOMS, NAPHTHYLOXY, PHENYLOXY, BENZYLOXY, ALKYLAMINO OF 1-6 CARBON ATOMS, CYCLOHEXYLAMINO, PHENYLAMINO, NAPHTHYLAMINO, BENZYLAMINO, ACETYLAMINO, ETHYLUREIDO, SULFONAMIDO, ALKYLSULFONAMIDO OF 1-6 CARBON ATOMS, PHENYLSULFONAMIDO, NAPHTHYSULFONAMIDO, CARBAMETHOXY, CARBOXAMIDO, HALO, CYANO, OR THE AFORESAID RADICALS WHEREIN THE ALKYL PORTION OF THE AROMATIC RING IS FURTHER SUBSTITUTED BY HALO, HYDROXY, CYCLOHEXYL, CYCLOPENTYL, ALKOXY OF 1-6 CARBON ATOMS BENZYLOXY, PHENYLOKY, ALKOXYCARBONYL OR 1-6 CARBON ATOMS IN THE ALKYL PORTION, CYANO, AMINOCARBONYL, AMINO ALKYLAMINO OR 1-6 CARBON ATOMS DIALKYLAMINO OF 1-6 CARBON ATOMS IN EACH ALKYL PORTION, ACETYLAMINO, SULFONYLAMINO, MERCAPTO, ALKYLMERCAPTO OF 1-6 CARBON ATOMS, OR PHENYLMERCAPTO; AND ADDITIONALLY WHEREIN THE AROMATIC RING IS SUBSTITUTED BY ALKYL OF 1-6 CARBON ATOMS;R1 IS ALKYL OR 1-6 CARBON ATOM, PHENYLALKYL OR 1-6 CARBON ATOMS IN THE ALKYL PORTION, OR THE AROMATIC RADICALS WHEREIN THE ALKYL PORTION OR THE AROMATIC RING FURTHER SUBSTITUTED BY HALO, HYDROXY CYCLOHEXYL, CYCLOPENTYL, ALKOXY OR 1-6 CARBON ATOMS, BENZYLOXY, PHENYLOXY, ALKOXYCARBONYL OR 1-6 CARBON ATOMS IN THE ALKYL PORTION, CYANO, AMINOCARBONYL, AMINO, ALKYLAMINO OF 1-6 CARBON ATOMS, DIALKYLAMINO OF 1-6 CARBON ATOMS IN EACH ALKYL PORTION, ACETYLAMINO, SULFONYLAMINO, MERCAPTO, ALKYLMERCAPTO OF 1-6 CARBON ATOMS, OR PHENYLMERCAPTO; AND ADDITIONALLY WHEREIN THE AROMATIC RING IS SUBSTITUTED BY ALKYL OF 1-6 CARBON ATOMS; R2 IS HYDROGEN, ALKYL OF 1-6 CARBON ATOMS, CYANO, CARBOXAMIDO, ALKYLSULFONYL OR 1-6 CARBON ATOMS, OR SAID ALKYL OR ALKYLSULFONYL WHEREIN THE ALKYL PORTION IS FURTHER SUBSTITUTED BY HALO, HYDROXY, CYCLOHEXYL, CYCLOPENTYL, ALKOXY OF 1-6 CARBON ATOMS, BENZYLOXY, PHENYLOXY, ALKOXYCARBONYL OR 1-6 CARBON ATOMS IN THE ALKYL PORTION, CYANO, AMINOCARBONYL, AMINO, ALKYLAMINO OF 1-6 CARBON ATOMS, DIALKYLAMINO OF 1-6 CARBON ATOMS, IN EACH ALKYL PORTION, ACETYLAMINO, SULFONYLAMINO, MERCAPTO, ALKYLMERCAPTO OF 1-6 CARBON ATOMS, OR PHENYLMERCAPTO; R3 IS ALKYL OR 1-6 CARBON ATOMS, PHENYLALKYL OR 1-6 CARBON ATOMS IN THE ALKYL PORTION, OR THE AFORESAID RADICALS WHEREIN THE ALKYL PORTION OR THE AROMATIC RING IS FURTHER SUBSTITUTED BY HALO, HYDROXY, CYCLOHEXYL, CYCLOPENTYL, ALKOXY OR 1-6 CARBON ATOMS, BENZYLOXY, PHENYLOXY, ALKOXYCARBONYL OF 1-6 CARBON ATOMS IN THE ALKYL PORTION, CYANO, AMINOCARBONYL, AMINO ALKYLAMINO OF 1-6 CARBON ATOMS, DIALKYLAMINO OF 1-6 CARBON ATOMS IN EACH ALKYL PORTION, ACETYLAMINO, SULFONYLAMINO, MERCAPTO, ALKYLMERCAPTO OF 1-6 CARBON ATOMS, OR PHENYLMERCAPTO; AND ADDITIONALLY WHEREIN THE AROMATIC RING IS SUBSTITUTED BY ALKYL OF 1-6 CARBON ATOMS; AND AN (-) IS AN ANION.

United States Patent 3,850,913 NOVEL BASIC INDOLINE DYESTUFFS Hubertus Psaar, Leverkusen, Germany, assignor to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed June 22, 1972, Ser. No. 265,319 Claims priority, application Germany, June 22, 1971, P 21 30 790.4 Int. Cl. C09b 23/00 US. Cl. 260240.8 12 Claims ABSTRACT OF THE DISCLOSURE Basic dyestuffs of the formula R- -CH3 CH3 R1 CH3 R, An() Rs in which R means hydrogen, an alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aryloxy or aralkoxy radical, an alkyl-, aryl-, aralkylor acyl-amino radical, an arylsulphonamido, alkylsulphonamido, sulphonamido, carboxylic acid ester, carboxamido, or acyl radical, halogen or cyano;

R means an alkyl, aralkyl or acyl radical;

R means hydrogen, an alkyl group, cyano, a carboxylic acid ester, carboxamido or alkylsulphonyl group;

R means an alkyl or aralkyl radical;

R means hydrogen, an alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aryloxy or aralkoxy group, an alkyl-, aryl-, aralkylor acyl-amino group, an arylsulphonamido, alkylsulphonamido, sulphonamido, carboxylic acid ester, carboxamido or acyl radical, halogen or cyano; and

An means an anion.

The subject matter of the invention further comprises processes for the production of these dyestutfs and the use of the latter for the dyeing and printing of natural and synthetic materials, as well as the materials dyed and printed with these dyestuffs.

The term alkyl radical refers to a saturated or olefinic-unsaturated aliphatic radical with 1 to 6 carbon atoms, which may contain non-ionic substituents and/or carboxyl groups, for example, the methyl, ethyl, nand iso-propyl, n-, isoand tert.-butyl radicals and the vari- 3,850,913 Patented Nov. 26, 1974 ous isomeric pentyl and hexyl radicals, as well as vinyl, allyl or propenyl radicals.

Cycloalkyl radicals means, for example, cyclopentyl and cyclohexyl radicals, which may be substituted by nonionic radicals and/ or carboxyl groups.

Aryl radicals are, for example, phenyl radicals which may be substituted by non-ionic substituents and/or car boxyl groups, and their fusion products, such as the naphthalene radical which may be substituted by non-ioni substituents and/or carboxyl groups.

Aralkyl radicals are, for example, alkyl radicals substituted by aryl or heteryl radicals.

Heteryl radicals are 5- or 6-membered unsaturated heterocyclic rings, such as the thienyl, pyridyl, pyrrolyl, indolyl-(Z), indolyl-(S), benzothiazolyl-(Z) or benzoxazolyl-(Z) radicals.

Non-ionic substituents in the meaning of the present invention are the non-dissociating substituents customary in the chemistry of dyestuffs, such as halogen, alkyl, cycloalkyl, hydroxy, alkoxy, aralkoxy, cycloalkoxy, aryloxy, acyloxy, acyl, alkoxycarbonyl, amidocarbonyl, nitrile, amino, alkylamino, acylamino, sulphonylamino, sulphonyl, amidosulphonyl, mercapto, alkylrnercapto and arylmercapto groups.

Suitable anionic radicals An are the organic and inorganic anions customary for cationic dyestuifs.

Inorganic anions are, for example, fluoride, chloride, bromide and iodide; perchlorate, hydroxyl; radicals of S-containing acids, such as hydrogen sulphate, sulphate, disulphate and aminosulphate; radicals of nitrogen-0x0- acids, such as nitrate; radicals of oxoacids of phosphorus, such as dihydrogen phosphate, hydrogen phosphate and metaphosphate; radicals of carbonic acid, such as hydrogen carbonate and carbonate; other anions of oxoacids and complex acids, such as methosulphate, ethosulphate, hexafluorosilicate, cyanate, thiocyanate, hexacyanoferrate- (II), hexacyanoferrate-(III), triand tetrachlorozincate, triand tetrabromozincate, stannate, borate, divanadate, tetravanadate, molybdate, tungstate, chromate, bichromate and tetrafluoroborate; as well as anions of esters of boric acid, such as the glycerol ester of boric acid, and of esters of phosphoric acid, such as methyl phosphate.

Organic anions are, for example, anions of saturated or unsaturated aliphatic, cycloa'liphatic, aromatic andheterocyclic carboxylic acids and sulphonic acids, such as radicals of acetic acid, chloro acetic acid, cyano acetic 'acid, hydroxy acetic acid, amino acetic acid, methylamino acetic acid, aminoethyl-sulphonic acid, methylaminoethylsulphonic acid, propionic acid, n-butyric acid, i-butyric acid, 2-methyl-butyric acid, 2-ethyl-butyric acid, dichloro acetic acid, trichloro acetic acid, trifluoro acetic acid, 2-

chloropropionic acid, 3-chloropropionic acid, 2 chloro-.

butyric acid, Z-hydroxypropionic acid, 3 hydroxypropionic acid, O-ethylglycolic acid, thioglycolic acid, glyceric acid, malic acid, dodecyl-tetraethylene glycol etherpropionic acid, 3-(nonyloxy)-propionic acid, 3 (isotridecyloxy) propionic acid, 3 (isotridecyloxy)-diethylene glycol-ether-propionic acid, ether-propionic acid of the alcohol mixture with 6 to 10 carbon atoms, thioacetic acid, 6-benzoyl-amino-2-chloro-caproic acid, nonylphenob: tetraethylene glycol ether-propionic acid, nonylphenol-diethylene glycol ether-propionic acid, dodecyl-tetraethyleneglycol ether-propionic acid, phenoxy acetic acid, nonylphenoxy acetic acid, rz-valeric acid, i-valeric acid, 2,2,2- trimethyl acetic acid, n-caproic acid, 2 ethyl-n-caproic acid, stearic acid, oleic acid, ricinoleic, palmitic acid, npelargonic acid, lauric acid; a mixture of aliphatic carboxylic acids with 9 to 11 carbon atoms (versatic acid,

911 of Shell), a mixture of aliphatic carboxylic acids with 15 to 19 carbon atoms (-versatic acid 1519 of Shell); coconut fatty acid first runnings, undecane-carboxylic acid, n-tridecane-carboxylic acid and a coconut fatty acid' mixture; acrylic acid, methacrylic acid, crotonic acid, propargylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid; isomer mixture of 2,2,4- and 2,4,4-trimethyl-adipic acid; sebacic acid, isosebacic acid (isomer mixture), tartaric acid, citric acid, glyoxylic acid, dimethylether-a,a'- dicarboxylic acid, methylene-bis-thioglycolic acid, dimethyl-sulphide-6 -dicarboxylic acid, 2,2 dithio-di-npropionic acid, fumaric acid, maleic acid, itaconic acid, ethylene bis iminoacetic acid, nitrilosulphonic acid, methane-sulphonic acid, ethane sulphonic acid, chloromethane-sulphonic acid, 2-chloroethane-sulphonic acid and 2 hydroxyeth'ane sulphonic acid; mersolate, i.e. C C paraffin-sulphonic acid, obtained by chlorosulphonation of paraffin oil.

Suitable anions of cycloaliphatic carboxylic acids are, for example, the anions of cyclohexane-carboxylic acid, cyclohexene-3 carboxylic acid; and anions of araliphatic monocarboxylic acids are, for example, anions of phenylacetic acid, 4-methylphenylacetic acid and mandelic acid.

Suitable anions of aromatic carboxylic acids are, for example, the anions of benzoic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 4-tert.-butylbenzoic acid, 6-chloro-3-nitro-benzoic acid, 2,4-dinitro- S-chlorobenzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 6-chloro-3-nitro-benzoic acid, 2,4 dinitrobenzoic acid, 3,4-dinitrobenzoic acid, 3,5 dinitrobenzoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4- hydroxybenzoic acid, 2-mercaptobenzoic acid, 4-nitro-3- methylbenzoic acid, 4-aminobenzoic acid, 5-nitro-2-hydroxybenzoic acid, 3-nitro 2 hydroxybenzoic acid, 4- methoxybenzoic acid, 3-nitro-4-methoxybenzoic acid, 4- chloro-3-hydroxybenz0ic acid, 3-chloro-4-hydroxybenzoic acid, 5-chloro-2-hydroxy-3-methylbenzoic acid, 4 ethylmercapto-2 chlorobenzoic acid, 2 hydroxy 3 methylbenzoic acid, 6 hydroxy 3 methylbenzoic acid, 2- hydroxy-4 methylbenzoic acid, 6-hydroxy-2,4 dimethylbenzoic acid, 6-hydroxy-3-tert.-buty1benzoic acid, phthalic acid, tetrachlorophthalic acid, 4-hydroxyphthalic acid, 4- methoxyphthalic acid, isophthalic acid, 4-chloroisophthalic acid, S-nitroisophthalic acid, terephthalic acid, nitroterephthalic acid and diphenylcarboxylic acid-( 3,4), o-vanillic acid, 3-sulphobenzoic acid, benzene-tetracarboxylic acid-(1,2,4,5,naphthalene-tetracarboxylic acid (1,4,5,8 biphenylcarboxylic acid-(4), abietic acid, phthalic acid mono-n-butyl ester, terephthalic acid monomethyl ester, 3 hydroxy 5,6,7,8-tetrahydronlaphthalene carboxylic acid- (2), 2-hydroxynaphthoic acid-(1) and anthraquinone-carboxylic acid-(2) Suitable anions of heterocyclic carboxylic acids are, for example, the anions of furoic acid, dehydromucic acid, indolyl-(3)-acetic acid.

Suitable anions of aromatic sulphonic acid are, for example, the anions of benzene-sulphonic acid, benzenedisulphonic acid-(1,3), 4-chlorobenzene-sulphonic acid, 3- nitrobenzene-sulphonic acid, 6-chloro-3-nitrobenzene-sulphonic acid, toluene-sulphonic acid-(4), toluene sulphonic acid-(2), toluene-w-sulphonic acid, 2 chlorotoluene-sulphonic acid-(4), l-hydroxybenzene-sulphonic acid, n-dodecylbenzene sulphonic acid, 1,2,3,4 tetrahydronaphthalene-sulphonic acid (6), naphthalene-sulphonic acid-(1), naphthalene disulphonic acid-(1,4) or -(1,5), naphthalene-trisulphonic acid-(1,3,5), naphthol (1)-sulphonic acid-(2), S-nitro-naphthalene-sulphonic acid-(2),

8-aminonaphthalene-sulphonic acid-(1), stilbene-sulphonic acid-(2,2') and biphenyl-sulphonic acid-(2).

A suitable anion of a heterocyclic sulphonic acid is, for example, the anion of quinoline-sulphonic acid-(5).

Further suitable anions are those of aryl-sulphinic, -phosp-honic and -phosphonous acids, such as benzenesulphinic and benzene phosphonic acid.

Colourless or almost colourless anions are preferred. For dyeing from an aqueous solution, those anions are 4 preferred which do not too strongly impair the watersolubility of the dyestuffs.

Among the claimed dyestuffs, special attention may be drawn to those of the formula alkoxy, aryloxy or aralkoxy group, an alkyl-, aryl-,

aralkylor acylamino group, an arylsulphonamido,

'alkylsulphonamido, sulphonamido, carboxylic acid ester, carboxamido or acyl radical, halogen or cyano; R means a lower alkyl or an aryl-lower alkyl radical; and An means an anion.

Valuable dyestuffs according to the present invention are the compounds of the formula Re- CH CH3 CH J: An() H=CH \IIT/ R7 J and of the formula N CH3 CHa Rs H=OH \N/ J R1 (IV) in which R means a lower alkoxy, benzyloxy, lower alkylamino,

benzylamino or lower alkyl-carbonylamino group;

R means a lower alkyl or benzyl radical;

R means a lower alkoxy, benzyloxy, lower alkylamino, benzylamino or lower alkyl-carbonylamino group; and

An means an anion.

Particularly valuable are the dyestulfs of the formula Rg0 CH3 CH3 CH; om An() AH=CH and of the formula in which R means a C -C alkyl or a benzyl group; R means methyl or cyanoethyl;

R means a C -C alkyl or benzyl group; and An means an anion.

The dyestuffs of the general formula (I) are prepared by either reacting compounds of the general formula R CH3 H with aldehydes of the formula R4 -CH3 CCH=O R2 R3 (VIII) or with their functional derivatives, in water and/or an organic solvent, with the addition of an acidic condensation agent, or by reacting formamides of the formula CH3 R L-CH:

\N LE1 II-1:0 with compounds of the formula R CH OH \N I R2 3 (X) in an organic solvent, with the addition of'an acidic condensation agent. The solvent or condensation agent yields the anion An which can be exchanged after the reaction for any other anion by known methods.

In the formulae (VII) to (X) the radicals R to R have the same meaning as in formula (I).

The dyestuffs of the general formula (II) can be prepared not only by the above methods but also by reacting compounds of the formula CH3 R |-CH:4

H (XI) or compounds of the formula CH3 R I OH;

N (XII) with compounds (X) and with formic acid in an organic solvent, with the addition of an acidic condensation agent.

In the formulae (XI) and (XII) the symbols R and R have the same meaning as in formula (II).

Cir

Compounds serving as solvents for the preparation of the dyestuffs (I) are, for example, water, alcohols, acetonitrile, dimethyl formamide, benzene, chloroform, chlorobenzene, dichlorobenzene, toluene, xylene, or acetic acid, formic acid, sulphuric acid or phosphoric acid.

Suitable acidic condensation agents are, for example, hydrogen chloride, sulphuric acid, phosphoric acid, acetic acid, phosphorus oxychloride, thionyl chloride, phosgene, ZnCl BF or acetic acid anhydride.

Components of the formula (VII) suitable for carrying out the process are, for example,

2,3 3-trimethylindoline, 5-methyl-2,3 3-trimethylindoline, 5-methoxy-2,3, 3-trimethylindoline, 5-cthoxy-2,3 ,3-trimethylindoline, S-propyloxy-Z, 3,3-trimethylindoline, 5-butoxy-2,3,3-trimethylindoline, 5-benzyloxy-2,3,3-trimethylindoline, S-benzylamino-Z,3,3-trimethylindoline, 5-ethylamino-2,3,3-trimethylindoline, S-isopropylamino-Z,3,3-trimethylindoline, 5-acetylamino-2,3 ,3-trirnethylindoline, 5-methylsulphonylamino-Z,3 ,3-trimethylindoline, S-methoxy-Z-phenylethyl-3,B-dimethylindoline, 5-methoxy-2-(4-rnethyloxyphenylethyl)-3,3-dimethy1- indoline, S-methoxy-Z-(4-methylphenylpropyl)-3,3-dimethylindoline, S-methoxy-Z-phenylbutyl-3,3-dimethylindoline, 5-methoxy-2-acetyl-3 ,3-dimethylindoline, 5-methoxy-2-cyanomethyl-3 ,3-dimethylindoline, 5-methoxy-2-ethylcarboxyethyl-3, 3-dimethylindoline, 5 -methoxy-2-methylcarboxyethylamido-3 ,B-dimethylindoline.

Suitable components of the formula (VIII) are, for example, l,3,3-trimethyl-2-methylene-indoline-w-aldehyde, 1,3,3-trimethyl-5-methoxy-2-methylene-indoline-waldehyde, 1,3,3-trimethyl-5-ethoxy-2-methylene-indoline-waldehyde, 1,3,3-trimethyl-5-propyloxy-2-methylene-indoline-waldehyde, 1,3,3-trimethyl-S-butyloxy-Z-methylene-indoline-waldehyde, 1,3,3-trimethyl-5-benzyloxy-2-methylene-indoline-waldehyde, 1,3,3,S-tetramethyl-Z-methylene-indoline-w-aldehyde, 1,3,3-trimethyl-5-benzylamino-2-methylene-w-aldehyde, 1,3,3-trimethyl-S-dimethylamino-2-methylene-indolinew-aldehyde, l,3,3-trimethyl-5-acetylamino-Z-methylene-indoline-waldehyde, 1,3,3-trimethyl-S-methylsulphonylamino-Z-methyleneindoline-w-aldehyde, l,3,3-trimethyl-5-chloro-2methylene-indoline-waldehyde, 1,3,3-trimethyl-5-cyano-2-methylene-indoline-w-aldehyde, l,3,3-trimethyl-5-methoxycarbonyl-Z-methylene-indolinew-aldehyde, 1,3,3-trimethyl-5-nitro-2-ethylene-in-doline-w-aldehyde, 1-ethyl-3,3-dimethyI-Z-methylene-indoline-w-aldehyde, 1-cyanoethyl-3,3-dimethyl-Z-methylene-indoline-waldehyde, l-benzyl-3,3-dimethyl-2-methylene-indoline-w-aldehyde, 1,3,3-trimethylZ-methylene-indoline-w-cyano-w-aldehyde, 1,3,3-trimethyl-S-methoxy-Z-methylene-indoline-wcyano-w-aldehyde, 1-benzyl-3,3-dimethylindoline-w-aldehyde.

Suitable components of the formula (IX) are, for example,

7 N-formyl-2,3 ,3-trimethylindoline, N-frmyl-2,3,3 ,S-tetramethylindoline, N-formyl--methoxy-2,3 ,3-trimethylindoline, N-formyl-5-eth0xy-2,3,3 -trimethylindoline, N-formyl-5-propyloxy-2,3 ,3-trimethylindoline, N-formyl-5-butyloxy-2,3,3-trimethylindoline, N-formyl-S-benzyloxy-Z, 3,3-trimethylindoline, N-formyl-5-benzylformylaminc-2, 3,3-trimethylindoline, N-formyl-S-acetylamino-Z,3,3-trimethylindoline, N -formyl-5 -methoxy-2-phenylethyl-3 ,B-dimethylindoline, N-formyl-5-methoxy-2- (4-methylphenylpropyl -3,3-

dimethylindoline, N-formyl-S-methoxy-2-(4-methoxyphenylethyl)-3,3

dimethylindoline, N-formyl-5-chloro-2,3 ,3-trimethylind0line, N-formyl-5-cyano-2,3,3-trimethylindoline, N-formyl-S-carbomethoxy-Z,3,3-trimethylindoline.

Suitable components of the formula (XII) are 2,3 ,3-trimethyl-indolenine, 2,3,3,5-tetramethyl-indolenine,

2,3 ,3-trimethyl-S-methoxy-indolenine, 2,3,3-trimethyl-5-ethoxy-indolenine, 2,3,3-trimethyl-S-propyloxy-indolenine, 2,3,3-trimethyl-S-butyloxy-indolenine, 2,3 ,3-trimethyl-S-benzyloxy-indolenine, 2, 3 ,3-trimethyl-5-acetylamino-indolenine, 2,3,3-trimethyl-5-chloroind0lenine, 2,3,3-trimethyl-S-cyanoindolenine, 2-benzyl-3 ,3-dimethylindolenine, 2-phenylethyl-3,3-dimethyl-indolenine.

The dyestuffs according to the invention are suitable for the dyeing, printing and dyeing in the mass of natural, semi-synthetic and synthetic materials, mainly for materials consisting of polyacrylonitrile or of copolymers of 8 acrylonitrile with other vinyl compounds, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl alcohol, acrylic and methacrylic acid esters and amides, as, dicyanoethylene; or of acid-modified aromatic polyester. Acid-modified aromatic polyesters are, for example, polycondensation products of sulphoterephthalic acid and ethylene glycol, i.e. polyethylene glycol terephthalates containing sulphonic acid groups (type Dacron 64 of E. I. du Pont de Nemours and Company), such as are described in Belgian patent specification No. 549,179 and US. patent specification No. 2,893,816. The dyestuffs are also suitable for dyeing acid-modified polyamides.

The dyeings and prints on these materials have excellent fastness properties, especially fastness to light. The dyestuffs are characterised by their unusual colour intensity and have a very good resist effect in respect of wool, cotton and non-acid-modified polyesters and polyamides.

The parts given in the examples are parts by weight.

EXAMPLE 1 21 parts Smethoxy-2,3,3-trimethyl-indolenine were hydrogenated with 0.5 parts of Raney nickel as catalyst and 2.5 parts methanol at 170 C. and 150 atm. excess pressure in an autoclave. The catalyst was filtered off. 25 parts glacial acetic acid and 22.5 parts 1,3,3-trimethyl-2-methylene-indolenine w-aldehyde were then added, and the mixture was stirred at room temperature for 4 hours. The solution was stirred into 500 parts of a 3% sodium chloride solution and 10 parts of concentrated hydrochloric acid. After one hour, the dyestuff was filtered off with suction and dried at C. in a vacuum. It has the formula OH: CHaO CH3 N CHa CH3- 01 H:CH N/ (1H3 indoline-w-cyano-w-aldehyde.

9 EXAMPLE 2 38.4 parts 2,3,3 trimethyl-indolenine were stirred in 300 parts chlorobenzene and 50 parts formic acid at 120 C. for 2 hours. 220 parts chlorobenzene were distilled off, and 49 parts 5 methoxy-l,3,3-trimethyl-2-methylene-indoline and 40 parts phosphorus oxychloride were added to the residue at 60 C. The mixture was stirred at 60 C. for 2 hours and then added to a solution of 100 parts sodium acetate in 1000 parts of water. The chlorobenzene was separated, the dyestufi was precipitated from the aqueous phase with sodium chloride and dried in a vacuum The 5-methoxy-2-phenylethyl-3,3-dimethyl-ind0line was prepared according to Example 1 by catalytic hydrogenation.

When the 5 methoxy-Z-phenylethyl-3,S-dimethylindoline is replaced with 5-methoxy-2,3,3-trimethylindoline,

then the dyestuff described in Example 1 is obtained.

EXAMPLE 4 19 parts N-formyl-Z,3,3-trimethyl-indoline and 23 parts 5 acetylamino-1,3,3-trimethyl-Z-methyIene-indoline were stirred in 100 parts xylene with 15.6 parts phosphorus at 70 C. It has the formula -CHg N LOH:

I CH;

and dyes fibres of polyacrylonitrile as well as acid-modified polyester and polyamide fibres in brilliant yellow shades.

When the 2,3,3-trimethyl-indolenine is replaced with 5- methoxy 2,3,3-trimethyl-indolenine and the 5-methoxy- 1,3,3 trimethyl-Z-methyelne-indolenine is replaced with 1,3,3 trimethyl-2-methylene-indoline, then the dyestufl described in Example 1 is ob tained.

i The following table describes dyestuffs which were prepared according to Examp le 2. The table contains the components of the dyestuffs and the shades of the latter on polyacrylonitrile fibres.

oxychloride at 60 C. for 2 hours. 30 parts methanol were then added. The dyestuif was filtered off with suction and recrystallised from water. It has the formula and dyes polyacrylonitrile fibres in fast yellow shades.

The N-formyl-2,3,S-trimethyl-indoline was prepared from 2,3,3-trimethyl-indolenine by reaction with formic acid in chlorobenzene at 120 C. and isolated by distillation.

When the 5-acetylamino-1,3,3-trimethyl-2-methyleneindoline is replaced with S-methoxy-1,3,3-trimethyl-2- methylene-indoline, then the dyestutf described in Example 2 is obtained.

Indolentne base Aldehyde Shade indoline.

Greenish yellow. Do.

EXAMPLE 3 26.9 parts 5-methoxy-2-phenylethyl-3,3-dimethyl-indoline and 20.2 parts 1,3,3-tr

imethyl-Z-methylene-indolinew-aldehyde were stirred in 150 parts chloroform with 15.6

parts phosphorus oxychloride at 60 C. for one hour.

The chloroform was distilled off, and the dyestutf was recrystallised from water with the addition of active charcoal. It has the formula 0 H3 01130 CH3 F Cl(-) CH3 7 0 H: C H \N and dyes polyacrylonitrile fibres in clear yellow shades.

EXAMPLE 5 21.8 parts S-acetylamino-1,3,3-trimethyl-indoline and 20.2 parts 1,3,3-trimethyl-Z-methylene-indoline-w-aldehyde were stirred in 40 parts methanol and 10 parts'of concentrated hydrochloric acid at room temperature for 3 hours. The solution was stirred into 600 parts of a 5% sodium chloride solution. After 3 hours, the dyestuff was filtered off with suction and dried at 40 C. in a vacuum. It has the formula and dyes polyacrylonitrile fibers in fast yellow shades.

11 The S-acetylamino-2,3,3-trimethyl-indoline was prepared according to Example 1 by catalytic hydrogenation. The following dyestuffs were prepared according to Example 5:

Indoline base Aldehyde Shade 5-methoxy-2-(4mcthylphenylethyl)- 1 ,3,3-trimethyl 2- Grcenish 3,3-dirnethyl-indoline. methylenc-inyellow.

doline-w-aldehydo 5-methoxy-2-(methylcarboxyethylo Do.

amide) -3,3-dirnethyl-indoline. 1 -isopropy1amin02,3,3-trin1ethyldo Do.

indoline. 5-bonzylarnino-2,3,3-trimcthyldo D o.

indoline. 5-ethy1amin0'2,3,3-trimethy1-indoline do Do. 5-cyclohexylamino-2,3,3-trimethyldo Do.

indoline. 5-ethy1nricdo-2,3,3-trimethyl-indolinc do Do.

EXAMPLE 6 21.9 parts N-formyl-S-methoxy-Z,3,3-trimethyl-indoline were dissolved in 150 parts benzene. 12 parts phosgene were introduced at room temperature, and the mixture was stirred at 30 C. for one hour. 21 parts S-methoxy- 1,3,3-trimethyl-2-methylene-indoline were then added, and the mixture was stirred at 60 C. for 2 hours. 100 parts benzene were distilled off, the dyestuff was filtered off with 25 suction and recrystallised from water. It has the formula C11 0 OH3 OH I 3 \N CH3 CHa- OCI'I3 CU JJH-CH N and dyes polyacrylonitrile fibres in fast yellow shades.

EXAMPLE 7 EXAMPLE 8 Acid-modified polyglycol terephthalate fibres are introduced at 20 C. in a liquor ratio of 1:40 into an aqueous bath which contains, per litre, 3-10 g. sodium sulphate, 0.1-1 g. oleyl polyglycol ether (50 mol ethylene oxide), 0-15 g. dimethylbenzyl dodecylammonium chloride and 0.15 g. of the dyestuff described in Example 1 and which was adjusted to pH 4-5 with the aid of acetic acid. The bath is heated to 100 C. within 30 minutes and kept at the same temperature for minutes. The fibres are subsequently rinsed and dried. A greenish yellow dyeing of very good fastness properties is obtained.

EXAMPLE 9 In a dyeing beaker of 500 ml. capacity which is placed on a heated water bath, 0.055 g. of the dyestulf described in Example 1 are pasted with 20 times this amount of hot water with the addition of some acetic acid, and dissolved with hot water. 0.5 g. of the reaction product of 50 mol ethylene oxide with 1 mol oleyl alcohol are also added to the dyeing liquor which is made up with cold water to a volume of 500 ml. The pH value of the dyeing liquor is adjusted to 4.5-5 with the aid of acetic acid or sodium acetate.

10 'g. of piece goods of acid-modified polyamide are continuously moved about in this dyebath while the temperature is raised to C. within 15 minutes. The material is dyed at boiling temperature for 1520 minutes, 7 5

rinsed with cold water, and subsequently dried. very fast greenishyellow dyeing is obtained.

EXAMPLE 10 A fabric of polyacrylonitrile is printed with a printing paste which was prepared in the following way;

330 parts of hot water are poured over 30 parts of the 1. Basic dyestuff of the formula wherein R and R independently of each other, are hydrogen, alkyl of 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl, naphthyl, phenylalkyl of 1-6 carbon atoms in the alkyl portion, alkoxy of 16 carbon atoms, naphthyloxy, phenyloxy, benzyloxy, alkylamino of 1-6 carbon atoms, cyclohexylamino, phenylamino, naphthylamino, benzylamino, acetylamino, ethylureido, sulfonamido, alkylsulfonamido of 1-6 carbon atoms, phenylsulfonamido, naphthylsulfonamido, carbomethoxy, carboxamido, halo, cyano, or the aforesaid radicals wherein the alkyl portion or the aromatic ring is further substituted by halo, hy-

droxy, cyclohexyl, cyclopentyl, alkoxy of l-6 carbon atoms, benzyloxy, phenyloxy, alkoxycarbonyl of 1-6 carbon atoms in the alkyl portion, cyano, aminocarbonyl, amino, alkylamino of 1-6 carbon atoms, dialkylamino of 1-6 carbon atoms in each alkyl portion, acetylamino, sulfonylamino, mercapto, alkylmercapto of 1-6 carbon atoms, or phenylmercapto; and additionally wherein the aromatic ring is substituted by alkyl of 1-6 carbon atoms;

R is alkyl of 1-6 carbon atoms, phenylalkyl of I -6 R is hydrogen, alkyl of 1-6 carbon atoms, cyano,

carboxamido, alkylsulfonyl of 1-6 carbon atoms, or said alkyl or alkylsulfonyl wherein the alkyl portion is further substituted by halo, hydroxy, cyclohexyl, cyclopentyl, alkoxy of 1-6 carbon atoms, benzyloxy, phenyloxy, alkoxycarbonyl of 1-6 carbon atoms in the alkyl portion, cyano, aminocarbonyl, amino, alkylamino of 1-6 carbon atoms, dialkylamino of 1-6 carbon atoms, in each alkyl portion, acetylamino, sulfonylamino, mercapto, alkylmercapto of 1-6 carbon atoms, or phenylmercapto;

R is alkyl of 1-6 carbon atoms, phenylalkyl of 1-6 carbon atoms in the alkyl portion, or the aforesaid radicals wherein the alkyl portion or the aromatic ring is further substituted by halo, hydroxy, cyclohexyl, cyclopentyl, alkoxy of 1-6 carbon atoms, benzyloxy, phenyloxy, alkoxycarbonyl of 16 carbon atoms in the alkyl portion, cyano, aminocarbonyl, amino, alkylamino of 1-6 carbon atoms, dialkylamino of l-6 carbon atoms in each alkyl portion, acetylamino, sulfonylamino, mercapto, alkylmercapto of 1-6 carbon atoms, or phenylmercapto; and additionally wherein the aromatic ring is substituted by alkyl of l-6 carbon atoms; and

An is ananion.

2. The dyestuff of Claim 1 wherein R is hydrogen, methyl, methoxy, ethoxy, propoxy,

butoxy, benzyloxy, chloro, cyano, acetylamino, isopropylamino, benzylamino, ethylamino, cyclohexylamino, or ethylureido;

R is methyl, phenylethyl, or 4-methylphenylethyl;

R is hydrogen or cyano;

R is hydrogen, methyl, cyanoethyl, or benzyl;

R is hydrogen, methyl, methoxy, ethoxy, propoxy, butoxy, benzyloxy, chloro, cyano, carbomethoxy, or acetylamino; and

Am" is an anion.

3. Basic dyestuffs of the general formula R r' CH1 CH; CH3- I An() H=CH- \blr/ R1 J and of the general formula CH3 l+) CH CH1 R, I An H=CH- R1 J in which R and R mean alkoxy of 1-6 carbon atoms, benzyloxy, alkylamino of 1-6 carbon atoms, benzylamino, or acetylamino;

R means alkyl of 16 carbon atoms or benzyl;

and

An means an anion.

4. Basic dyestuffs of the general formula in which R means a C -C alkyl or a benzyl group; R means methyl or cyanoethyl;

14 R means a C -C alkyl or a benzyl group; An means an anion. 5. A basic dyestuff of the formula I CH: i

CH;O -om \N CH: VCH:\

H=-=CH- \N/ CH: 6. A basic dyestuff of the formula 1 CH3 I a oflH5-cmo orr,

CH3 \N -0H3 3m Cl() JJH=CH-\\N/ l on, 7. A basic dyestufi? of the formula CHa--CO-NH- -CH3 CH3 cna emf/Q ore l CH=CH cm 8. A basic dyestutf of the formula CHa CH3 Lon, on, -oom 01H N H=CH- CH1 9. A basic dyestuff of the formula (3 I CH3 CH i z CHa O HauH5 (31H JJH=CH N 5H: J

10. A basic dyestuff of the formula F CH3 I CH,

CH, \N CH; CHJ---- NH-CO-CHa 01H J1H=CH- 11. Dyestutf of Claim 3 of the formula CHa Re I OH:

crr, ens- I oH=oH f B:

wherein t R is alkoxy of 1-6 carbon atoms, benzyloxy, alkylamino of 1-6 carbon atoms, benzylamino, or acetylamino;

7 l 5 1 6 R is alkyiof 1' 6 carbon atoms or benzyl; and References Cited An is an anion. P N 12. Dyestuff of Claim 4 of the formula UNITED STATES ATE TS CH m 2,077,063 4/1937 Wolff 26O240.8 2,155,447 4/1939 ROh et a] 260240.8 Rg-O ken; 5

' CH1 FOREIGN PATENTS \N c11, om- 666,081 10/1938 Germany 260 240.8

$H=eH 1 JOHN D. RANDOLPH, Primary Examiner N 0 us. 01. X.R. wherein 8-62, 177 AB, 178 R, 179; 260240.1, 319.1, 326.11 R,

R is alkyl of 1-4 carbon atoms or benzyl; 326.16 R is methyl or cyanqethyl; and 15 An is an anion. 

1. BASIC DYESTUFF OF THE FORMULA 